高含硫气藏单质硫溶解度测试方法及预测模型

针对高含硫气藏单质硫溶解度测量准确度低的问题,基于溶剂溶解原理,建立高含硫气藏单质硫溶解度测试实验装置及实验方法,实现了某气藏含硫气样中的单质硫溶解度的测定.研究结果表明:高含硫气藏地层温度为40.0～98.9℃,地层压力为15.0～49.8 MPa,其单质硫标准状况下的溶解度为0.001～0.968 g/m3;单质硫...     

高效液相色谱法测定生物脱硫溶液中单质硫

生物脱硫作为一种新的天然气净化手段,具有净化度高、流程简单、环境污染少、能耗低等特点,在低碳经济发展和环境保护等方面显示出潜在的优势。主要讨论了利用高效液相色谱法测定生物脱硫溶液中的单质硫。用有机溶剂萃取生物脱硫循环液中的单质硫,前处理后在指定高效液相色谱条件下检测单质硫浓度,形成了一套简单可行的测定生物脱硫溶液中单质硫的方法。该方法的检测限为0.04mg/L,加标回收率为103.00%,满足生物脱硫溶液中单质硫的测定需要。同时,讨论了生物脱硫溶液中其余硫副产物对单质硫的干扰。     

IMPREGNATION AND RECOVERABILITY OF ELEMENTAL SULFUR IN COAL USING THE PERCHLOROETHYLENE DESULFURIZATION PROCESS

ABSTRACT

During the perchloroethylene extraction process, C-S bond cleavage reactions occur, which liberate labile sulfur from the organic matrix of coal into the solvent medium i.e., perchloroethylene, where it is dissolved and extracted. In this paper, the effect of impregnation of elemental sulfur in raw coal on its forms of sulfur analyses has been investigated. The effect of the same sulfur-impregnated coal on its organosulfur extractability has also been explored. Studies were conducted to observe whether the impregnated elemental sulfur was fully recoverable by the perchloroethylene extraction process. It was observed that sulfur can be very easily impregnated into the microstructure of coal. On the basis of tests on raw and impregnated coals, based on ASTM D-2492 standard, the impregnated sulfur reflects mostly in the form of organic sulfur. The impregnated sulfur which appears in the form of organic sulfur is fully recoverable via the perchloroethylene extraction     

Thermodynamic and quantum chemical study of the transformations and operation mechanism of molybdenum catalysts under hydrogenation conditions

Structural transformations and the mechanism of the operation of molybdenum-containing catalysts under hydrogenation conditions have been studied by chemical thermodynamics and quantum chemistry methods, as well as the role of sulfur compounds in this process. It has been shown that molybdenum disulfide, an effective hydrogenation catalyst, is produced via the reaction of molybdenum oxide with hydrogen sulfide, not elemental sulfur. It has been concluded that the introduction of elemental sulfur (which is subsequently converted into hydrogen sulfide) or an organic sulfur compound into the reaction system, on one hand, facilitates the transformation of molybdenum oxides into MoS₂ and, on the other hand, yields the effective reagent H₂S, which takes part in the disproportionation reactions involving hydrogen transfer.     

AN EXPERIMENTAL APPROACH OF ELEMENTAL SULFUR DEPOSITION IN CARBONATE OIL RESERVOIRS

The existence of sulfur compounds in crude oils creates many problems of sulfur deposition in the vicinity of the wellbore hole, in well completion and/or production equipment, and in producing reservoir rocks. The major objectives of this experimental study are to investigate the influences of oil flow rate, initial sulfur concentration of crude oil, and reservoir rock permeability on elemental sulfur plugging in carbonate oil reservoirs. To achieve these objectives, actual crude oils were de-asphaltened to eliminate the effect of asphaltene deposition. Ten dynamic flow experiments were conducted using two actual crude oils of 0.78 and 1.67% sulfur concentrations. Viscosity of crude oils of different sulfur concentrations was measured under different conditions of temperature. The crude oils were flooded through actual carbonate cores of different permeability in the range of 2.34-28.16 millidarcy and under different flow rates of 0.5, 1.0, 1.5, and 2.0 cc/min. In-situ sulfur deposited was measured using Scanning Electron Microscopy (SEM) to provide the amount of sulfur deposited along the core samples. The results indicated that crude oil of higher sulfur concentration has higher viscosity than that of one of lower concentration. The deposition of elemental sulfur does not take place at the low rate of 0.50 cc/min, starts at 1.0 cc/min and increases as the flow rate increases up to 1.50 and 2.00 cc/min, respectively. In addition, the higher sulfur concentration of the crude oil increases the deposition of sulfur in carbonate oil reservoirs. The results also showed that permeability of carbonate reservoir rocks has a severe effect on sulfur deposition since carbonate rocks of higher permeability do not experience the problem of elemental sulfur deposition while the problem is more severe for lower permeability rocks. In addition, the depositional rate is accelerated rapidly as the rock permeability decreases. The obtained results of this study have important interest in identification of the most important factors affecting the elemental sulfur precipitation in heterogeneous carbonate oil reservoirs and robust implications in the development of reservoir simulation models.     

高含硫碳酸盐岩酸压气井硫沉积规律研究

硫沉积是高含硫气藏开发过程中的常见现象,不仅给生产设备带来严重的安全隐患,也容易造成地层堵塞,是影响该类气藏安全高效开发的重要因素之一，但目前国内外对地层中硫沉积条件的研究都是基于简单的静态环境,预测结果往往与实际存在较大差异。在综合考虑基岩和裂缝渗流空间特征以及气流水动力对析出的硫颗粒运移影响的基础上,建立了描述碳酸盐岩酸压气井生产过程中硫沉积预测模型。结果表明:流体水动力是建立硫沉积预测模型必须考虑的因素之一；硫在基岩中的沉积主要发生在距井底和靠近裂缝面相对较小的区域,且沿井底向裂缝纵深方向和垂直于裂缝向外延伸的方向上,硫沉积量和沉积速率均呈递减下降的趋势；硫在裂缝中的沉积距井底距离越近,硫沉积量越大且沉积速率相对较快；无论是基岩或裂缝中的硫沉积,随着生产时间的延长,其沉积速率呈加速变化趋势。     

硫吸附和地层水存在下的单质硫沉积规律研究

在酸性气藏中,元素硫的沉积会减小气体的流动空间,其进一步的沉积会堵塞气体的流通通道,导致气井产量降低。为加强对高含硫气藏地层中单质硫沉积规律的认识,进行了以下理论研究：考虑元素硫吸附效应,建立一套系统的高含硫气藏元素硫地层沉积预测模型,并利用该模型对某油田实例进行计算;在地层水体存在的条件下,对硫沉积带来的影响。结果表明：当硫吸附效应或者地层水体存在时都会进一步加大硫沉积量,并且随着时间的推移,影响更加明显;在离气井较远的地带,硫吸附效应的影响更强。在理论研究的基础之上,进行了单质硫的聚集实验及其在岩石空隙中的分布规律实验。通过对实验结果的分析,硫的聚集是从纳米级的单质硫晶体聚集形成面状单质硫,再逐渐形成层状似的单质硫;单质硫在孔隙中的分布规律为：孔隙越大,硫沉积量越大。     

高含硫气田元素硫腐蚀机理及其评价方法

在高含硫气田的开发过程中,往往会出现元素硫的沉积现象。元素硫一旦沉积以后,很有可能堵塞采输管线并造成管材的严重腐蚀,对气田的正常生产影响很大。介绍了高含硫气田元素硫的来源及其危害,在此基础上分析了元素硫腐蚀的机理,详细论述了元素硫的腐蚀评价方法,并分析了每种方法的适用范围及其特点,根据国内现状,提出了具体的认识和建议。     

Experimental and numerical modeling of sulfur plugging in carbonate reservoirs

Sour gas, mainly in the form of hydrogen sulfide, is produced in large amounts from many oil and gas reservoirs in the United Arab Emirates. In addition to creating problems in production lines, the precipitation of elemental sulfur in vicinity of the wellbore is often reported to cause wellbore damage. While there have been several studies performed on the role of solid deposition in gas reservoirs, the role of sulfur deposition in oil reservoirs has not been investigated. This paper presents experimental results along with a comprehensive wellbore model that predicts sulfur precipitation as well as plugging. Two separate sets of experiments, one for a gas phase system and another for a crude oil system, were conducted to investigate the deposition of elemental sulfur in (linear) carbonate cores. The gas flow tests were conducted with elemental sulfur being carried with nitrogen through limestone cores. Changes in gas flow rate were monitored while the injection pressure was held constant. A series of experiments generated valuable data for plugging with elemental sulfur. X-ray diffraction tests provided evidence of sulfur deposition along the cores. The oil flow tests were carried out to observe sulfur precipitation and plugging in a carbonate core. The crude oil was de-asphalted before conducting these tests in order to isolate the effect of asphaltene plugging. Significant plugging was observed and was found to be dependent on flow rate and initial sulfur concentration. This information was used in a phenomenological model that was incorporated in the wellbore numerical model. The data for the numerical model were obtained from both test tube and oil flow experiments. By using a phenomenological model, the wellbore plugging was modeled with an excellent match (with experimental results).     

普光气田高含H2S天然气中硫含量及临界析出压力测定

普光气田高含H₂S天然气中的单质硫含量及临界析出压力是研究硫沉积问题首先要获取的两项关键参数,为此,基于气相色谱定量测定方法（外标标准曲线法）,利用从普光104-1井取得的井下气样、DMDS-DMA高效溶硫剂及气相色谱-质谱联用仪等样品和仪器,首次测定出普光气田高含H₂S天然气中的硫含量为0.78 g/m3（每标准立方米气样中的硫含量）,处于未饱和状态;进一步结合测定的不同压力下气样中硫的饱和含量变化曲线确定出临界析出压力为30.5 MPa;对比气田目前地层压力认为地层中尚未发生硫析出和沉积现象。      

高含硫气井新型胺类溶硫剂的性能研究:溶硫规律和再生性能(上)

针对造成高含硫气井内堵塞和腐蚀的硫沉积问题,研制出了以有机胺类化学溶剂为主剂,以物理溶剂为助剂,并配合乳化剂、硫化物催化剂、表面活性剂等的新型胺类溶硫剂体系,并对其溶硫性能以及溶硫后单质硫的分离回收性能进行了评价和研究。结果表明,新型胺类溶硫剂的溶硫过程迅速,在30min时基本完成,溶硫量达59.45g/100mL;升高溶硫温度、反应气氛中含有H2S或硫以粉状形态存在时,均有利于溶硫量的提高;溶硫体系中加水量为10%(φ)时,溶硫量保留率为74.27%;产物中加水可使单质硫析出回收,当加水量为900mL时,单质硫的回收率高达34.32%。     

考虑非平衡过程元素硫沉积对高含硫气藏储层伤害研究

元素硫沉积是高含硫气藏开发有别于常规气藏开发的一个重要研究内容.当地层压力下降时,元素硫溶解度下降使其沉积下来,沉积的元素硫会堵塞地层,从而降低地层孔隙度和渗透率.为了定量研究硫沉积对地层孔隙度和渗透率的影响,首先建立了元素硫沉积的伤害模型,然后利用该模型对一个实际高含硫气藏开发时由于元素硫沉积引起的地层孔隙度、渗透率和沉积含硫饱和度的动态变化进行了计算求解.通过实例计算发现:地层渗透率越低时越容易发生硫沉积,且硫沉积主要在井筒附近发生,当生产时间越长时,硫沉积的量越多,从而对地层的伤害越严重.     

IMPREGNATION AND RECOVERABILITY OF ELEMENTAL SULFUR IN COAL USING THE PERCHLOROETHYLENE DESULFURIZATION PROCESS

During the perchloroethylene extraction process, C-S bond cleavage reactions occur, which liberate labile sulfur from the organic matrix of coal into the solvent medium i.e., perchloroethylene, where it is dissolved and extracted. In this paper, the effect of impregnation of elemental sulfur in raw coal on its forms of sulfur analyses has been investigated. The effect of the same sulfur-impregnated coal on its organosulfur extractability has also been explored. Studies were conducted to observe whether the impregnated elemental sulfur was fully recoverable by the perchloroethylene extraction process. It was observed that sulfur can be very easily impregnated into the microstructure of coal. On the basis of tests on raw and impregnated coals, based on ASTM D-2492 standard, the impregnated sulfur reflects mostly in the form of organic sulfur. The impregnated sulfur which appears in the form of organic sulfur is fully recoverable via the perchloroethylene extraction     

元素硫与其它硫化物共存时铜片腐蚀性能的考察

考察了元素硫的铜片腐蚀程度，碱洗后腐蚀程度的变化，以及硫醇，二硫化物对元素的硫腐蚀的影响，并对元素硫和硫醇共存时，在脱臭前后腐蚀现象的变化进行了研究，同时比较了不同脱臭方法脱除元素硫的效果。结果表明，元素硫在很低浓度下就可产生严重的铜片腐蚀，碱洗不能很好地除去元素硫，只有在加入助溶剂后才能脱除。不同结构的硫醇和二硫化物对元素硫的腐蚀产生不同的影响，使腐蚀铜片出现不同的多彩色。脱臭过程中，元素硫能否     

酸性气田的元素硫沉积、腐蚀与治理研究

含H2S天然气在生产和集输过程中都可能发生元素硫沉积,引起井筒、地面集输管线堵塞,危害巨大,是含硫气藏生产过程中必须解决的关键难题之一。本文介绍了酸性气田的元素硫来源,元素硫沉积的影响因素,沉积机理,预测模型,并指出向井口或管线注入溶硫剂是当今解决硫堵问题的有效措施之一。潮湿或含水汽的元素硫与金属直接接触可能导致设备发生灾难性的腐蚀问题,腐蚀机理复杂。本文还总结了元素硫腐蚀控制技术及沉积治理方面的研究进展。     

高含硫气田元素硫沉积及其腐蚀

高含硫气田在开发和维护过程中容易出现硫沉积并引发严重硫腐蚀,由此造成的管道堵塞、管道腐蚀穿孔、设备损毁失效都会严重影响油气田的正常生产。为此,分析了高含硫气田中元素硫的来源：①烃类硫酸盐的热化学反应;②高温高压下H₂S的缩聚反应;③硫烷的分解;④离子多硫化物的分解;⑤氧气对H₂S的氧化;⑥溶解在液态烃中的元素硫。阐述了硫沉积的发生机理：元素硫能溶解在酸性气体中,主要是溶解在硫化氢中。剖析了硫腐蚀机理：包括以元素硫的水解为基础的催化机理、水解机理、电化学机理和直接反应机理。探讨了硫腐蚀的影响因素：温度、压力、氯离子、硫的存在形式和流速等。最后建议：针对硫沉积区的特殊环境,开展多介质多相混合流体中管线的硫腐蚀机理研究,并建立其腐蚀模型。该研究成果可为高含硫油气田的安全有效开发提供参考。     

气相色谱法测定液化气中的元素硫

液化气中的元素硫被萃取到溶剂甲苯中，再用气相色谱测定催化裂化汽油中的元素硫方法测定萃取液中的元素硫。该方法成功地用于液化气铜片腐蚀不合格的原因分析。     

NiMo/Al2O3上H2还原脱除烟气中SO2和NO探索

采用连续管式固定床反应器,在压力为常压、反应温度为100～600 ℃、无氧和含氧气氛下考察了NiMo/Al2O3催化剂上H2催化脱除SO2、NO的性能。结果表明：NiMo/Al2O3催化剂具有良好的同时脱硫脱硝的性能,SO2转化率、单质硫选择性均高于单独脱硫或单独脱硝时,但N2生成率低于单独脱硝时,其中SO2转化率随温度的升高而增高,直至达到100%;含氧气氛下的SO2转化率、单质硫选择性、N2生成率整体优于无氧气氛下的结果;SO2的存在对NO的吸附有抑制作用,NO的存在显著提高了SO2转化率和单质硫选择性。     

高速非达西流动时元素硫沉积模型研究

元素硫沉积是含硫气藏开发过程中广泛存在而又必须解决的难题之一。高含硫气藏一旦投入开发，地层压力会逐步下降，使得元素硫溶解度下降而沉积下来，沉积的元素硫会堵塞地层孔隙，降低渗流通道，影响气井产能。考虑了高含硫气体在近井地带作高速非达西流动，建立了硫的沉积模型，并利用该模型对实际气藏进行预测和对比研究，再通过实例计算发现，硫非瞬时平衡沉积比瞬时平衡沉积对地层的伤害更严重，高速非达西流动沉积比达西流动时对地层伤害更严重，认为在开发高含硫气藏时，必须合理选择开发速度，有效防止元素硫沉积。     

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根据国内某高含硫气田集输管线内高含H₂S（8%～16%）、CO₂（5%～10%）的高压腐蚀环境，分析了可能存在的腐蚀影响因素，并采用静态高温高压釜研究了H₂S、CO₂、温度、Cl-以及元素硫等不同腐蚀影响因素对20#钢的作用规律。结果表明，在试验研究的范围内，20#钢的腐蚀比较严重，腐蚀速率在0.348～2.559 mm/a之间，但温度、水中Cl-含量以及元素硫是影响20#钢腐蚀程度的主要因素：水中Cl-含量越高，20#钢的腐蚀速率越大；温度为40 ℃时20#钢的腐蚀速率相对较大；元素硫的存在会加速20#钢的失重腐蚀和点蚀，最大点蚀深度为4.867 mm/a。通过室内研究，建议现场采取适当的措施清除集输管线内沉积的元素硫，而且最好不要让集输管线的温度停留在40 ℃左右，以减轻对管线的腐蚀；此外，还要加强对高Cl-含量地层水汇集的集输管线的防腐蚀工作。